A direct test of the vibrationally adiabatic theory of chemical reactions

J. M. Bowman, Aron Kuppermann, J. T. Adams, Donald G Truhlar

Research output: Contribution to journalArticle

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Abstract

The adiabaticity assumption of the vibrationally adiabatic theory of chemical reactions in the zero-curvature approximation is directly tested for the collinear H + H2 reaction against calculations using exact wavefunctions. It is found that the symmetric stretch motion of the transition state is adiabatic to within 10% for total energies E ranging from 0.51 eV to 0.72 eV. For E below the zero-point energy of this symmetric stretch motion non-adiabaticity is substantial and is probably due to tunneling. For E above the first excited vibrational state energy of this symmetric stretch motion the adiabaticity assumption breaks down completely.

Original languageEnglish (US)
Pages (from-to)229-232
Number of pages4
JournalChemical Physics Letters
Volume20
Issue number3
DOIs
StatePublished - Jun 1 1973

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Wave functions
Electron energy levels
Chemical reactions
chemical reactions
zero point energy
vibrational states
breakdown
curvature
energy
approximation

Cite this

A direct test of the vibrationally adiabatic theory of chemical reactions. / Bowman, J. M.; Kuppermann, Aron; Adams, J. T.; Truhlar, Donald G.

In: Chemical Physics Letters, Vol. 20, No. 3, 01.06.1973, p. 229-232.

Research output: Contribution to journalArticle

Bowman, J. M. ; Kuppermann, Aron ; Adams, J. T. ; Truhlar, Donald G. / A direct test of the vibrationally adiabatic theory of chemical reactions. In: Chemical Physics Letters. 1973 ; Vol. 20, No. 3. pp. 229-232.
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